Resin additive composition and synthetic resin composition using same

ABSTRACT

Provided are: a resin additive composition containing a specific metal phosphate, which composition has excellent dispersibility in a resin even when made into a pellet form and exhibits a desired physical property improving effect when incorporated into a resin; and a synthetic resin composition using the same. The resin additive composition contains, with respect to 100 parts by mass of (A) sodium-2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate: 25 to 400 parts by mass of (B) a lithium phosphate compound represented by the following Formula (1); and 10 to 300 parts by mass of (C) a fatty acid metal salt represented by the following Formula (2). The component (C) is incorporated in an amount of 10 parts by mass to 50 parts by mass with respect to a total of 100 parts by mass of the components (A) and (B).

This application is a Continuation of copending application Ser. No.15/751,026 filed on Feb. 7, 2018, which is the U.S. National Phase ofPCT/JP2016/072391, filed Jul. 29, 2016, and which claims priority under35 U.S.C. § 119(a) to Application No. 2015-162740 filed in Japan, onAug. 20, 2015, the entire contents of all of which are expresslyincorporated by reference into the present application.

TECHNICAL FIELD

The present invention relates to a resin additive composition comprisinga specific metal phosphate. More particularly, the present inventionrelates to: a resin additive composition which comprises a specificlithium salt compound as a crystal nucleating agent component along witha metal phosphate and has improved dispersibility in resins byincorporating a fatty acid metal salt; and a synthetic resin compositioncomprising the same.

BACKGROUND ART

Synthetic resins, such as polyolefin resins (e.g., polyethylene,polypropylene and polybutene-1), polyester-based polymers (e.g.,polyethylene terephthalate and polybutylene terephthalate) andpolyamide-based polymers, have a slow crystallization rate after heatmolding. Therefore, not only there are such problems that the moldingcycle in processing is long, but also there are cases where theresulting molded article is deformed due to crystallization thatproceeds even after molding.

It is known that these drawbacks are attributed to the crystallinity ofthe synthetic resins and can be solved by allowing fine crystals to berapidly generated. As a method of generating a large number of finecrystals, for example, it is known to increase the crystallizationtemperature and/or to add a crystal nucleating agent, a crystallizationaccelerator or the like.

As the crystal nucleating agent, for example, metal carboxylates, suchas sodium benzoate, aluminum 4-tert-butylbenzoate, sodium adipate and2-sodium bicyclo[2.2.1]heptane-2,3-dicarboxylate; metal phosphates, suchas sodium-bis(4-tert-butylphenyl)phosphate,sodium-2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate andlithium-2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate; polyhydricalcohol derivatives, such as dibenzylidene sorbitol,bis(methylbenzylidene)sorbitol, bis(3,4-dimethylbenzylidene)sorbitol,bis(p-ethylbenzylidene)sorbitol and bis(dimethylbenzylidene)sorbitol;and amide compounds, such asN,N′,N″-tris[2-methylcyclohexyl]-1,2,3-propane tricarboxamide,N,N′,N″-tricyclohexyl-1,3,5-benzene tricarboxamide,N,N-dicyclohexylnaphthalene dicarboxamide and1,3,5-tri(2,2-dimethylpropaneamide)benzene, are known.

Among these crystal nucleating agents, as described in Patent Documents1 to 3, sodium-2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate isknown as a crystal nucleating agent having excellent effect of improvingthe physical properties of synthetic resins and is thus widely used.

Further, in Patent Document 4, a crystal nucleating agent compositionwhich containssodium-2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate, aluminum2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate and an aliphaticorganic acid metal salt is proposed.

Sodium-2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate is in apowder form; however, the use of such powder presents a concern foroperational safety associated with airborne particles. In addition,there is a problem that multiple kinds of resin additives in arbitraryamounts must be uniformly blended in accordance with variousapplications. Therefore, from the standpoints of measurability andoperability, there is a high demand for a resin additive compositionobtained by molding various resin additives into a pellet form. Forinstance, Patent Documents 5 and 6 propose resin additive compositionscomprising sodium-2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate.

RELATED ART DOCUMENTS Patent Documents

Patent Document 1: Japanese Unexamined Patent Application PublicationNo. S58-1736

Patent Document 2: Japanese Unexamined Patent Application PublicationNo. S59-184252

Patent Document 3: Japanese Unexamined Patent Application PublicationNo. S63-108063

Patent Document 4: Japanese Unexamined Patent Application PublicationNo. 2002-338820

Patent Document 5: Japanese Unexamined Patent Application PublicationNo. 2001-123021

Patent Document 6: Japanese Unexamined Patent Application PublicationNo. 2004-292710

SUMMARY OF THE INVENTION Problems to be Solved by the Invention

At compound manufacturers, generally, a resin additive is blended into apellet form resin and the resultant is molded and processed; however,when a powder form resin additive is used, since its specific gravity islargely different from that of the pellet form resin, it is difficult touniformly mix these components. Particularly,sodium-2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate is acompound that is hardly dispersed in a resin; therefore, it is demandedto improve the dispersibility thereof.

Moreover, whensodium-2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate is moldedinto a pellet form resin additive composition, there is also a problemthat desired physical properties are not likely to be attained due todeterioration of the dispersibility in a resin and the resin additivecomposition thus needs to be added in a large amount.

Studies have been conducted for improvement of the dispersibility ofsodium-2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate; however,none of the studies yielded a satisfactory result.

In view of the above, an object of the present invention is to provide:a resin additive composition comprising a specific metal phosphate,which composition has excellent dispersibility in a resin even when madeinto a pellet form and exhibits a desired physical property improvingeffect when incorporated into a resin; and a synthetic resin compositioncomprising the same.

Means for Solving the Problems

The present inventors intensively studied to discover that theabove-described problems can be solved by mixingsodium-2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate with aspecific lithium salt compound and a fatty acid metal salt, therebycompleting the present invention.

The resin additive composition of the present invention is characterizedby comprising, with respect to 100 parts by mass of (A)sodium-2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate: 25 to 400parts by mass of (B) a lithium phosphate compound represented by thefollowing Formula (1); and 10 to 300 parts by mass of (C) a fatty acidmetal salt represented by the following Formula (2),

wherein the content of the component (C) is in a range of 10 parts bymass to 50 parts by mass with respect to a total of 100 parts by mass ofthe components (A) and (B):

(wherein, R¹ to R⁴ each represent a linear or branched alkyl grouphaving 1 to 8 carbon atoms; and R⁵ represents an alkylidene group having1 to 4 carbon atoms)

(wherein, R⁶ represents an unsubstituted or hydroxy-substitutedaliphatic group having 1 to 40 carbon atoms; M represents a metal atom;and n is an integer of 1 to 4, representing a valence of the metal atomM).

It is preferred that the resin additive composition of the presentinvention further comprises (D) a phenolic antioxidant in an amount of10% by mass to 50% by mass with respect to a total amount.

The resin additive composition of the present invention is preferably ina pellet form.

The synthetic resin composition of the present invention ischaracterized by comprising, with respect to 100 parts by mass of asynthetic resin, the above-described resin additive composition of thepresent invention in a range of 0.001 to 5 parts by mass in terms of thetotal amount of the components (A) and (B).

Further, in the present invention, a synthetic resin composition whereinthe above-described synthetic resin is a polyolefin resin is preferred.

Effects of the Invention

According to the present invention, it is possible to realize a resinadditive composition comprising a specific metal phosphate, whichcomposition has excellent dispersibility in a resin even when made intoa pellet form and exhibits a desired physical property improving effectwhen incorporated into a resin; and a synthetic resin compositioncomprising the same.

MODE FOR CARRYING OUT THE INVENTION

Embodiments of the present invention will now be described in detail.

[(B) Lithium Phosphate Compound]

The lithium phosphate compound used in the present invention is acompound represented by the following Formula (1):

(wherein, R¹ to R⁴ each represent a linear or branched alkyl grouphaving 1 to 8 carbon atoms; and R⁵ represents an alkylidene group having1 to 4 carbon atoms).

Examples of the linear or branched alkyl group having 1 to 8 carbonatoms represented by R¹ to R⁴ in the Formula (1) include methyl, ethyl,propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl,tert-amyl, hexyl, heptyl, octyl, isooctyl, tert-octyl, and 2-ethylhexyl.In the present invention, a tert-butyl group is particularly preferred.

Examples of the alkylidene group having 1 to 4 carbon atoms representedby R⁵ in the Formula (1) include methylidene, ethylidene, propylidene,and butylidene.

Examples of a specific structure of the lithium phosphate compoundrepresented by the Formula (1) include those of the following compounds.It is noted here, however, that the present invention is not restrictedto the following compounds by any means.

In the present invention, the (B) lithium phosphate compound is used inan amount of 25 to 400 parts by mass, preferably 50 to 100 parts bymass, with respect to 100 parts by mass of (A)sodium-2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate. When theused amount of the (B) lithium phosphate compound is outside the rangeof 25 to 400 parts by mass, the effects of the present invention may notbe attained.

[(C) Fatty Acid Metal Salt]

The (C) fatty acid metal salt used in the present invention is acompound represented by the following Formula (2):

(wherein, R⁶ represents an unsubstituted or hydroxy-substitutedaliphatic group having 1 to 40 carbon atoms; M represents a metal atom;and n is an integer of 1 to 4, representing a valence of the metal atomM).

Examples of the aliphatic group having 1 to 40 carbon atoms representedby R⁶ in the Formula (2) include hydrocarbon groups such as alkylgroups, alkenyl groups, and alkyl groups in which two or moreunsaturated bonds are introduced, and, optionally, the aliphatic groupis substituted with a hydroxy group and/or is branched.

Specific examples thereof include saturated fatty acids, such as aceticacid, propionic acid, butyric acid, valeric acid, isovaleric acid,caproic acid, enanthic acid, caprylic acid, pelargonic acid, capricacid, 2-ethylhexanoic acid, undecylic acid, lauric acid, tridecylicacid, myristic acid, pentadecylic acid, palmitic acid, margaric acid,stearic acid, nonadecylic acid, arachidic acid, heneicosylic acid,behenic acid, tricosylic acid, lignoceric acid, cerotic acid, montanoicacid and melissic acid; linear unsaturated fatty acids, such as4-decenoic acid, 4-dodecenoic acid, palmitoleic acid, α-linolenic acid,linoleic acid, γ-linolenic acid, stearidonic acid, petroselinic acid,oleic acid, elaidic acid, vaccenic acid, eicosapentaenoic acid,docosapentaenoic acid and docosahexaenoic acid; and aromatic fatty acidssuch as trimesic acid. In the present invention, aliphatic groups having7 to 21 carbon atoms are preferred, and saturated fatty acids such asmyristic acid, stearic acid and 12-hydroxystearic acid are particularlypreferred.

Examples of the metal atom represented by M in the Formula (2) includealkali metals, magnesium, calcium, strontium, barium, titanium,manganese, iron, zinc, silicon, zirconium, yttrium, barium, and hafnium.Thereamong, alkali metals such as sodium, lithium and potassium can beparticularly preferably used.

In the present invention, the (C) fatty acid metal salt is, for example,preferably lithium stearate, sodium stearate, magnesium stearate, zincstearate, aluminum stearate, lithium myristate, magnesium behenate orlithium 12-hydroxystearate, more preferably lithium myristate, lithiumstearate or lithium 12-hydroxystearate, since these fatty acid metalsalts have good performance and can be relatively easily obtained.

The above-exemplified fatty acid metal salts can be produced by asynthesis method in which a carboxylic acid compound and a metalhydroxide are allowed to react with each other and the resultant issubsequently washed with water, dehydrated and dried (doubledecomposition method), or a synthesis method in which materials areallowed to directly react with each other without the use of water(direct method).

It is required that the (C) fatty acid metal salt be used in an amountof 10 to 300 parts by mass, preferably 20 to 200 parts by mass, withrespect to 100 parts by mass of (A)sodium-2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate, and in arange of 10 parts by mass to 50 parts by mass with respect to a total of100 parts by mass of the components (A) and (B). When the amount of the(C) fatty acid metal salt is less than 10 parts by mass with respect toa total of 100 parts by mass of the components (A) and (B), the effectsof the present invention may not be attained, whereas when the amount isgreater than 50 parts by mass, the performance (nucleator effect) of thecrystal nucleating agent components may be suppressed.

In addition to the above-described components (A) to (C), the resinadditive composition of the present invention may also contain anarbitrary and known resin additive(s) (e.g., a phenolic antioxidant, aphosphorus-based antioxidant, a thioether-based antioxidant, anultraviolet absorber, a hindered amine compound, a crystal nucleatingagent other than the components (A) and (B), a flame retardant, a flameretardant aid, a lubricant, a filler, a metallic soap, a hydrotalcite,an antistatic agent, a pigment and a dye) in such a range that does notmarkedly impair the effects of the present invention. Such known resinadditives may be incorporated into a synthetic resin separately from theresin additive composition of the present invention.

Particularly, it is preferred that the resin additive composition of thepresent invention further comprises (D) a phenolic antioxidant.

[(D) Phenolic Antioxidant]

The phenolic antioxidant used in the present invention is a knownantioxidant which contains a phenol skeleton in its molecular structure.Specific examples of such an antioxidant include2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol,stearyl(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,distearyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate,tridecyl-3,5-di-tert-butyl-4-hydroxybenzyl thioacetate,thiodiethylene-bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],4,4′-thiobis(6-tert-butyl-m-cresol),2-octylthio-4,6-di(3,5-di-tert-butyl-4-hydroxyphenoxy)-s-triazine,2,2′-methylene-bis(4-methyl-6-tert-butylphenol),bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butyric acid]glycol ester,4,4′-butylidene-bis(4,6-di-tert-butylphenol),2,2′-ethylidene-bis(4,6-di-tert-butylphenol),1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl]terephthalate,1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl)isocyanurate,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,3,5-tris[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate,tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propynyloxymethyl]methane,2-tert-butyl-4-methyl-6-(2-acryloyloxy-3-tert-butyl-5-methylbenzyl)phenol,3,9-bis[2-(3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy)-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane,and triethyleneglycol-bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate].

Thereamong,tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propynyloxymethyl]methaneis particularly preferred since it imparts a polyolefin resin withexcellent antioxidative effect and makes it easy to mold the resinadditive composition into a pellet form.

The amount of the phenolic antioxidant to be used is preferably adjustedin a range of 10% by mass to 50% by mass with respect to the totalamount of the resin additive composition. By using the phenolicantioxidant in an amount of 10% by mass or greater, it is made easy notonly to mold the resin additive composition into a pellet but also tomaintain the form of the pellet. Further, by using the phenolicantioxidant in an amount of 50% by mass or less, the effects of thepresent invention can be attained more favorably without hindering theactions and effects of the crystal nucleating agents provided by thecomponents (A) and (B).

Examples of the phosphorus-based antioxidant include triphenylphosphite, diisooctyl phosphite, heptakis(dipropyleneglycol)triphosphite, triisodecyl phosphite, diphenylisooctyl phosphite,diisooctylphenyl phosphite, diphenyltridecyl phosphite, triisooctylphosphite, trilauryl phosphite, diphenyl phosphite, tris(dipropyleneglycol)phosphite, diisodecylpentaerythritol diphosphite, dioleylhydrogen phosphite, trilauryl trithiophosphite, bis(tridecyl)phosphite,tris(isodecyl)phosphite, tris(tridecyl)phosphite, diphenyldecylphosphite, dinonylphenyl-bis(nonylphenyl)phosphite, poly(dipropyleneglycol)phenyl phosphite, tetraphenyl dipropylene glycol diphosphite,trisnonylphenyl phosphite, tris(2,4-di-tert-butylphenyl)phosphite,tris(2,4-di-tert-butyl-5-methylphenyl)phosphite,tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl]phosphite,tri(decyl) phosphite, octyldiphenyl phosphite, di(decyl)monophenylphosphite, distearyl pentaerythritol diphosphite, a mixture of distearylpentaerythritol and calcium stearate, alkyl(C10) bisphenol-A phosphite,di(tridecyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritoldiphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite,bis(2,4-dicumylphenyl)pentaerythritol diphosphite,tetraphenyl-tetra(tridecyl)pentaerythritol tetraphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,tetra(tridecyl)isopropylidene diphenol diphosphite,tetra(tridecyl)-4,4′-n-butylidene-bis(2-tert-butyl-5-methylphenol)diphosphite,hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butanetriphosphite, tetrakis(2,4-di-tert-butylphenyl)biphenylenediphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,(1-methyl-1-propanyl-3-ylidene)-tris(1,1-dimethylethyl)-5-methyl-4,1-phenylene)hexatridecylphosphite, 2,2′-methylene-bis(4,6-tert-butylphenyl)-2-ethylhexylphosphite, 2,2′-methylene-bis(4,6-di-tert-butylphenyl)-octadecylphosphite, 2,2′-ethylidene-bis(4,6-di-tert-butylphenyl)fluorophosphite,4,4′-butylidene-bis(3-methyl-6-tert-butylphenylditridecyl)phosphite,tris(2-[(2,4,8,10-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]ethyl)amine,3,9-bis(4-nonylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane,2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite,and poly-4,4′-isopropylidene diphenol C12-15 alcohol phosphite.

The phosphorus-based antioxidant is used in a range of preferably 0.001to 10 parts by mass, more preferably 0.01 to 0.5 parts by mass, withrespect to 100 parts by mass of a synthetic resin.

Examples of the thioether-based antioxidant includetetrakis[methylene-3-(laurylthio)propionate]methane,bis(methyl-4-[3-n-alkyl(C12/C14)thiopropionyloxy]-5-tert-butylphenyl)sulfide,ditridecyl-3,3′-thiodipropionate, dilauryl-3,3′-thiodipropionate,dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate,lauryl/stearyl thiodipropionate, 4,4′-thiobis(6-tert-butyl-m-cresol),2,2′-thiobis(6-tert-butyl-p-cresol), and distearyl disulfide.

The thioether-based antioxidant is used in a range of preferably 0.001to 10 parts by mass, more preferably 0.01 to 0.5 parts by mass, withrespect to 100 parts by mass of a synthetic resin.

Examples of the ultraviolet absorber include 2-hydroxybenzophenones,such as 2,4-dihydroxybenzophenone and5,5′-methylene-bis(2-hydroxy-4-methoxybenzophenone);2-(2-hydroxyphenyl)benzotriazoles, such as2-(2-hydroxy-5-methylphenyl)benzotriazole,2-(2-hydroxy-5-tert-octylphenyl) benzotriazole,2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole,2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole,2-(2-hydroxy-3,5-dicumylphenyl)benzotriazole,2,2′-methylene-bis(4-tert-octyl-6-benzotriazolylphenol), polyethyleneglycol esters of2-(2-hydroxy-3-tert-butyl-5-carboxyphenyl)benzotriazole,2-[2-hydroxy-3-(2-acryloyloxyethyl)-5-methylphenyl]benzotriazole,2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-butylphenyl]benzotriazole,2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-octylphenyl]benzotriazole,2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-butylphenyl]-5-chlorobenzotriazole,2-[2-hydroxy-5-(2-methacryloyloxyethyl)phenyl]benzotriazole,2-[2-hydroxy-3-tert-butyl-5-(2-methacryloyloxyethyl)phenyl]benzotriazole,2-[2-hydroxy-3-tert-amyl-5-(2-methacryloyloxyethyl)phenyl]benzotriazole,2-[2-hydroxy-3-tert-butyl-5-(3-methacryloyloxypropyl)phenyl]-5-chlorobenzotriazole,2-[2-hydroxy-4-(2-methacryloyloxymethyl)phenyl]benzotriazole,2-[2-hydroxy-4-(3-methacryloyloxy-2-hydroxypropyl)phenyl]benzotriazoleand 2-[2-hydroxy-4-(3-methacryloyloxypropyl)phenyl]benzotriazole;benzoates, such as phenyl salicylate, resorcinol monobenzoate,2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate,octyl(3,5-di-tert-butyl-4-hydroxy)benzoate,dodecyl(3,5-di-tert-butyl-4-hydroxy)benzoate,tetradecyl(3,5-di-tert-butyl-4-hydroxy)benzoate,hexadecyl(3,5-di-tert-butyl-4-hydroxy)benzoate,octadecyl(3,5-di-tert-butyl-4-hydroxy)benzoate andbehenyl(3,5-di-tert-butyl-4-hydroxy)benzoate; substituted oxanilides,such as 2-ethyl-2′-ethoxyoxanilide and 2-ethoxy-4′-dodecyloxanilide;cyanoacrylates, such as ethyl-α-cyano-β,β-diphenylacrylate andmethyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate; and a variety ofmetal salts and metal chelates, particularly salts and chelates ofnickel and chromium.

The ultraviolet absorber is used in a range of preferably 0.001 to 5parts by mass, more preferably 0.005 to 0.5 parts by mass, with respectto 100 parts by mass of a synthetic resin.

Examples of the hindered amine compound include

-   2,2,6,6-tetramethyl-4-piperidyl stearate,    1,2,2,6,6-pentamethyl-4-piperidyl stearate,-   2,2,6,6-tetramethyl-4-piperidyl benzoate,    bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,-   tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate,-   tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate,-   bis(2,2,6,6-tetramethyl-4-piperidyl).di(tridecyl)-1,2,3,4-butanetetracarboxylate,-   bis(1,2,2,6,6-pentamethyl-4-piperidyl).di(tridecyl)-1,2,3,4-butanetetracarboxylate,-   bis(1,2,2,4,4-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,-   1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol/diethyl    succinate polycondensate,-   1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6-morpholino-s-triazine    polycondensate,-   1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6-tert-octylamino-s-triazine    polycondensate,-   1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazine-6-yl]-1,5,8,12-tetraazadodecane,-   1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazine-6-yl]-1,5,8,12-tetraazadodecane,-   1,6,11-tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazine-6-yl]aminoundecane,-   1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazine-6-yl]amino    undecane,    bis{4-(1-octyloxy-2,2,6,6-tetramethyl)piperidyl}decanedionate,-   bis{4-(2,2,6,6-tetramethyl-1-undecyloxy)piperidyl)carbonate, and    TINUVIN® NOR™ 371 manufactured by Ciba Specialty Chemicals K.K.

The hindered amine compound is used in a range of preferably 0.001 to 5parts by mass, more preferably 0.005 to 0.5 parts by mass, with respectto 100 parts by mass of a synthetic resin.

Examples of the crystal nucleating agent other than the components (A)and (B) include metal carboxylates, such as sodium benzoate, aluminum4-tert-butylbenzoate, sodium adipate and2-sodium-bicyclo[2.2.1]heptane-2,3-dicarboxylate; polyhydric alcoholderivatives, such as dibenzylidene sorbitol,bis(methylbenzylidene)sorbitol, bis(3,4-dimethylbenzylidene)sorbitol,bis(p-ethylbenzylidene)sorbitol and bis(dimethylbenzylidene)sorbitol;and amide compounds, such asN,N′,N″-tris[2-methylcyclohexyl]-1,2,3-propane tricarboxamide,N,N′,N″-tricyclohexyl-1,3,5-benzene tricarboxamide,N,N-dicyclohexylnaphthalene dicarboxamide and1,3,5-tri(dimethylisopropoylamino)benzene.

As for the amount of such other crystal nucleating agent to be used, thetotal amount of crystal nucleating agents including the components (A)and (B) is preferably in a range of 0.001 to 5 parts by mass, morepreferably 0.005 to 0.5 parts by mass, with respect to 100 parts by massof a synthetic resin.

Examples of the flame retardant include aromatic phosphates, such astriphenyl phosphate, tricresyl phosphate, trixylenyl phosphate,cresyldiphenyl phosphate, cresyl-2,6-dixylenyl phosphate,resorcinol-bis(diphenylphosphate), (1-methylethylidene)-4,1-phenylenetetraphenyldiphosphate,1,3-phenylene-tetrakis(2,6-dimethylphenyl)phosphate, ADK STAB FP-500(trade name; manufactured by ADEKA Corporation), ADK STAB FP-600 (tradename; manufactured by ADEKA Corporation) and ADK STAB FP-800 (tradename; manufactured by ADEKA Corporation); phosphonates, such as divinylphenylphosphonate, diallyl phenylphosphonate and(1-butenyl)phenylphosphonate; phosphinates, such as phenyldiphenylphosphinate, methyl diphenylphosphinate and9,10-dihydro-9-oxa-10-phosphaphenanthlene-10-oxide derivatives;phosphazene compounds, such as bis(2-allylphenoxy)phosphazene anddicresylphosphazene; phosphorus-based flame retardants, such as melaminephosphate, melamine pyrophosphate, melamine polyphosphate, melampolyphosphate, ammonium polyphosphate, piperazine phosphate, piperazinepyrophosphate, piperazine polyphosphate, phosphorus-containingvinylbenzyl compounds and red phosphorus; metal hydroxides, such asmagnesium hydroxide and aluminum hydroxide; and bromine-based flameretardants, such as brominated bisphenol A-type epoxy resins, brominatedphenol novolac-type epoxy resins, hexabromobenzene, pentabromotoluene,ethylene-bis(pentabromophenyl), ethylene-bis-tetrabromophthalimide,1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane, tetrabromocyclooctane,hexabromocyclododecane, bis(tribromophenoxy)ethane, brominatedpolyphenylene ether, brominated polystyrene,2,4,6-tris(tribromophenoxy)-1,3,5-triazine, tribromophenyl maleimide,tribromophenyl acrylate, tribromophenyl methacrylate,tetrabromobisphenol A-type dimethacrylate, pentabromobenzyl acrylate andbrominated styrene. These flame retardants are preferably used incombination with a drip inhibitor such as a fluorocarbon resin and/or aflame retardant aid such as a polyhydric alcohol or hydrotalcite.

The flame retardant is used in a range of preferably 1 to 50 parts bymass, more preferably 10 to 30 parts by mass, with respect to 100 partsby mass of a synthetic resin.

The lubricant is added for the purposes of imparting the surface of theresulting molded article with lubricity and improving the damagepreventing effect. Examples of the lubricant include unsaturated fattyacid amides, such as oleic acid amide and erucic acid amide; saturatedfatty acid amides, such as behenic acid amide and stearic acid amide;butyl stearate; stearyl alcohols; stearic acid monoglyceride; sorbitanmonopalmitate; sorbitan monostearate; mannitol; stearic acid; hardenedcastor oil; and ethylenebis stearic acid amide. These lubricants may beused individually, or two or more thereof may be used in combination.

The lubricant(s) is/are used in a range of preferably 0.01 to 2 parts bymass, more preferably 0.03 to 0.5 parts by mass, with respect to 100parts by mass of a synthetic resin.

Examples of the filler include talc, mica, calcium carbonate, calciumoxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide,magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate,glass powder, glass fibers, clays, dolomite, silica, alumina, potassiumtitanate whiskers, wollastonite and fibrous magnesium oxysulfate, andany of these fillers can used by appropriately selecting the particlesize (the fiber diameter, fiber length and aspect ratio in the case of afibrous filler). Further, the filler to be used can be subjected to asurface treatment as required.

The filler is used in a range of preferably 0.01 to 80 parts by mass,more preferably 1 to 50 parts by mass, with respect to 100 parts by massof a synthetic resin.

As the metallic soap, salts formed by a metal, such as magnesium,calcium, aluminum or zinc, and a saturated or unsaturated fatty acid,such as lauric acid, myristic acid, palmitic acid, stearic acid, behenicacid or oleic acid, can be used.

The metallic soap is used in a range of preferably 0.001 to 10 parts bymass, more preferably 0.01 to 5 parts by mass, with respect to 100 partsby mass of a synthetic resin.

The hydrotalcite is a complex salt compound which is known as a naturalor synthetic product and composed of magnesium, aluminum, hydroxylgroups, a carbonate group and arbitrary crystal water, and examplesthereof include hydrotalcites in which some of the magnesium or aluminumatoms are substituted with other metal such as an alkali metal or zinc;and hydrotalcites in which the hydroxyl group(s) and/or carbonate groupis/are substituted with other anionic group(s), specificallyhydrotalcites represented by the following Formula (3) in which a metalis substituted with an alkali metal. In addition, as an Al—Lihydrotalcite, a compound represented by the following Formula (4) can beused as well.

Mg_(x1)Zn_(x2)Al₂(OH)_(2(x1+x2)+4)(CO₃)pH₂O  (3)

(wherein, x1 and x2 each represent a number that satisfies theconditions represented by the following equations; and p represents 0 ora positive number:

0≤x2/x1<10, 2≤(x1+x2)≤20)

[Li_(1/3)Al_(2/3)(OH)₂].[A^(q-) _(1/3q) .pH₂O]  (4)

(wherein, A^(q−) represents an anion having a valence of q; and prepresents 0 or a positive number)

Further, the carbonate anion in the above-described hydrotalcites may bepartially substituted with other anion.

In these hydrotalcites, the crystal water may be dehydrated, and thehydrotalcites may be coated with, for example, a higher fatty acid suchas stearic acid, a higher fatty acid metal salt such as alkali metaloleate, a metal organic sulfonate such as alkali metaldodecylbenzenesulfonate, a higher fatty acid amide, a higher fatty acidester, or a wax.

The hydrotalcite may be a naturally-occurring or synthetic hydrotalcite.Examples of a method of synthesizing such a compound include knownmethods that are described in Japanese Examined Patent Publication No.S46-2280, Japanese Examined Patent Publication No. S50-30039, JapaneseExamined Patent Publication No. S51-29129, Japanese Examined PatentPublication No. H3-36839, Japanese Unexamined Patent ApplicationPublication No. S61-174270, Japanese Unexamined Patent ApplicationPublication No. H5-179052 and the like. Further, the above-exemplifiedhydrotalcites can be used without any restriction on the crystalstructure, crystal particle and the like.

The hydrotalcite is used in a range of preferably 0.001 to 5 parts bymass, more preferably 0.05 to 3 parts by mass, with respect to 100 partsby mass of a synthetic resin.

Examples of the above-described antistatic agent include cationicantistatic agents, such as fatty acid quaternary ammonium ion salts andpolyamine quaternary salts; anionic antistatic agents, such as higheralcohol phosphates, higher alcohol EO adducts, polyethylene glycol fattyacid esters, anionic alkyl sulfonates, higher alcohol sulfates, higheralcohol ethylene oxide adduct sulfates and higher alcohol ethylene oxideadduct phosphates; nonionic antistatic agents, such as polyhydricalcohol fatty acid esters, polyglycol phosphates and polyoxyethylenealkyl allyl ethers; and amphoteric antistatic agents, such as amphotericalkyl betaines (e.g., alkyldimethylamino acetic acid betaines) andimidazoline-type amphoteric activators. These antistatic agents may beused individually, or two or more thereof may be used in combination.

The antistatic agent(s) is/are used in a range of preferably 0.03 to 2parts by mass, more preferably 0.1 to 0.8 parts by mass, with respect to100 parts by mass of a synthetic resin.

As the above-described pigment, a commercially available pigment can beused as well, and examples thereof include PIGMENT RED 1, 2, 3, 9, 10,17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144,149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202,209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240 and 254; PIGMENTORANGE 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62,64, 65 and 71; PIGMENT YELLOW 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60,73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125,126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166,168, 175, 180 and 185; PIGMENT GREEN 7, 10 and 36; PIGMENT BLUE 15,15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 22, 24, 56, 60, 61, 62 and 64; andPIGMENT VIOLET 1, 19, 23, 27, 29, 30, 32, 37, 40 and 50.

Examples of the above-described dye include azo dyes, anthraquinonedyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes,acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinolinedyes, nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes andcyanine dyes, and a plurality of these dyes may be used in combination.

The resin additive composition of the present invention is preferably ina pellet form. As a method of producing the resin additive compositionin a pellet form, a mixture obtained by mixing the above-describedcomponents (A) to (C) and phenolic antioxidant with other additive(s)optionally incorporated as required can be mixed in the presence of thephenolic antioxidant in a molten state. The processing conditions, theprocessing equipments and the like are not restricted at all, and anywell-known and commonly used processing method and processing equipmentscan be used.

Specific examples of the production method include a disk pelletermethod and an extrusion method. In the present invention, an extrusionmethod which can easily achieve mass production and exhibits excellentmaintenance of the pellet form is preferred. Further, the processingtemperature in the extrusion method is preferably in a range of from notlower than the melting point of the phenolic antioxidant to 50° C.higher than the melting point. When the processing temperature is lowerthan the melting point of the phenolic antioxidant, the resulting pelletmay have insufficient form stability, whereas when the processingtemperature is higher than the melting point of the phenolic antioxidantby more than 50° C., the fluidity of the resulting resin additivecomposition is increased and this may make it difficult to mold theresin additive composition.

(Powdering Rate)

It is preferred that the pellet form resin additive composition of thepresent invention is capable of maintaining a product shape duringtransportation. Specifically, when 100 g of a sample thereof that doesnot pass through a sieve having a mesh opening size of 1.39 mm is placedin a 500-ml plastic container and subjected to 4-hour shaking at anamplitude of 40 mm and a shaking rate of 300 cycles/min, it is desiredthat the amount of the sample passing through the sieve having a meshopening size of 1.39 mm be preferably less than 1% by mass, morepreferably less than 0.5% by mass.

The synthetic resin composition of the present invention comprises, withrespect to 100 parts by mass of a synthetic resin, the above-describedresin additive composition of the present invention in a range of 0.001to 5 parts by mass, preferably 0.005 to 0.5 parts by mass, in terms ofthe total amount of the components (A) and (B). When the total amount ofthe components (A) and (B) is less than the above-described range, theeffects of the crystal nucleating agents may not be attained, whereaswhen the total amount of the components (A) and (B) is greater than theabove-described range, an effect corresponding to the added amount maynot be attained, which is uneconomical, and the components (A) and (B)may appear on the surface of the resulting molded article anddeteriorate the outer appearance. In both of these cases, the expectedeffects of the present invention are not attained.

In cases where the resin additive composition of the present inventionis blended with a synthetic resin and the resultant is molded, a knownmolding method can be employed to perform the molding. For example, whenthe synthetic resin is a thermoplastic resin, a molded article can beobtained by injection molding, extrusion molding, blow molding, vacuummolding, inflation molding, calender molding, slush molding, dipmolding, foam molding or the like.

Meanwhile, when the synthetic resin is a curable resin that can be curedby heat, light, radiation or the like, a molded article can be obtainedby compression molding, injection molding, low-pressure molding,laminate molding or the like.

Examples of the synthetic resin used in the present invention includeα-olefin polymers, such as polypropylene, high-density polyethylene,low-density polyethylene, linear low-density polyethylene, polybutene-1and poly-3-methylpentene; polyolefins and copolymers thereof, such asethylene-vinyl acetate copolymers, ethylene-ethyl acrylate copolymers,ethylene-methyl acrylate copolymers, ethylene-acrylic acid copolymers,ethylene-methacrylic acid copolymers, ethylene-vinyl alcohol copolymersand ethylene-propylene copolymers; halogen-containing resins, such aspolyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene,chlorinated polypropylene, polyvinylidene fluoride, chlorinated rubbers,vinyl chloride-vinyl acetate copolymers, vinyl chloride-ethylenecopolymers, vinyl chloride-vinylidene chloride copolymers, vinylchloride-vinylidene chloride-vinyl acetate ternary copolymers, vinylchloride-acrylate copolymers, vinyl chloride-maleate copolymers andvinyl chloride-cyclohexylmaleimide copolymers; petroleum resins;coumarone resins; polystyrene; polyvinyl acetate; acrylic resins;copolymers (e.g., AS resins, ABS resins, MBS resins and heat-resistantABS resins) composed of styrene and/or α-methylstyrene with othermonomer (e.g., maleic anhydride, phenylmaleimide, methyl methacrylate,butadiene or acrylonitrile); linear polyesters, such as polymethylmethacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral,polyethylene terephthalate and polybutylene terephthalate; polyamides,such as polyphenylene oxide, polycaprolactam and polyhexamethyleneadipamide; thermoplastic resins and blends thereof, such aspolycarbonate, polycarbonate/ABS resin, branched polycarbonate,polyacetal, polyphenylene sulfide, polyurethane, triacetyl cellulose andcellulose-based resins; and thermosetting resins, such as phenol resins,urea resins, melamine resins, epoxy resins and unsaturated polyesterresins. Further, the synthetic resin may be an elastomer, such as anisoprene rubber, a butadiene rubber, an acrylonitrile-butadienecopolymer rubber or a styrene-butadiene copolymer rubber. Thesesynthetic resins may be used individually, or two or more thereof may beused in combination.

As the synthetic resin used in the present invention, a polyolefin resinselected from ethylene homopolymers, propylene homopolymers,ethylene/propylene block or random copolymers and non-ethyleneα-olefin/propylene block or random copolymers is preferred because theeffects of the present invention are prominently attained.

Examples of the use of the synthetic resin composition of the presentinvention include automobile materials, such as bumpers, dash boards andinstrument panels; housing applications, such as refrigerators, laundrymachines and vacuum cleaners; household articles, such as tablewares,buckets and bath goods; miscellaneous goods such as toys; storageapplications such as tanks; molded articles such as storage containers;films; and fibers.

Examples

The present invention will now be described more concretely by way ofexamples thereof; however, the present invention is not restrictedthereto by any means.

Using a Henschel mixer (trade name: FM200, manufactured by Mitsui MiningCo., Ltd.; at a blade rotation speed of 1,000 rpm for 1 minute), 100parts by mass of a polypropylene block copolymer having a melt flow rateof 25 g/10 min was mixed with 0.1 parts by mass oftetrakis[methylene-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propionate]methaneas a phenolic antioxidant, 0.1 parts by mass oftris(2,4-di-tert-butylphenyl)phosphite as a phosphorus-basedantioxidant, 0.05 parts by mass of calcium stearate as a neutralizer andthe respective resin additive compositions shown in Table 1 or 2 below.Then, using twin screw extruder (PCM-30, manufactured by Ikegai Corp.),the resulting mixtures were each granulated under processing conditionsof a temperature of 240° C. and a screw speed of 160 rpm, wherebypellets of synthetic resin compositions were obtained.

(Flexural Modulus)

Using an injection molding machine (EC100-2A; manufactured by ToshibaMachine Co., Ltd.), the thus obtained pellets were each injection-moldedat an injection temperature of 230° C. and mold temperature of 50° C. toprepare test pieces of 10 mm in width, 80 mm in length and 4 mm inthickness. Immediately after the injection molding, the thus obtainedtest pieces were conditioned for at least 48 hours in an incubatorhaving an inner temperature of 23° C. and subsequently subjected to themeasurement of flexural modulus using a bending tester.

The results thereof are shown in Table 1 below.

(Crystallization Temperature)

A small amount of each pellet obtained above was cut out, and thecrystallization temperature thereof was measured using a differentialscanning calorimeter (DIAMOND, manufactured by PerkinElmer Co., Ltd.).As for the measurement method, in a chart obtained by heating thesubject pellet from room temperature to 230° C. at a rate of 50° C./min,maintaining the pellet for 10 minutes and then cooling the pellet to 50°C. at a rate of −10° C./min, the temperature at which endothermicreaction formed a peak top was defined as the crystallizationtemperature.

The results thereof are shown in Table 2 below.

TABLE 1 Amount of (A) + Amount of (A) + (B) (B) + (C) with with respectto respect to Evaluation Resin additive composition 100 parts by 100parts by Flexural (A) (B) (C) mass of resin mass of resin modulus [partsby mass] [parts by mass] [parts by mass] [parts by mass] [parts by mass][MPa] Example 1-1 Compound A*¹ Compound B*² LIM*³ 0.02 0.03 1,520 100 8050 Example 1-2 Compound A Compound B LIM 0.02 0.03 1,510 100 100 50Example 1-3 Compound A Compound B LIM 0.02 0.03 1,500 100 187.5 62.5Example 1-4 Compound A Compound B LIM 0.02 0.03 1,510 100 100 100Comparative — — — — 0 1,190 Example 1-1 Comparative Compound AComparative LIM 0.02 0.03 1,410 Example 1-2 100 Compound 1*⁴ 62.5 187.5Comparative — Compound B LIM 0.02 0.03 1,380 Example 1-3 100 50Comparative Compound A — LIM 0.02 0.03 1,400 Example 1-4 100 50Comparative Compound A Compound B — 0.03 0.03 1,370 Example 1-5 100 100Comparative Compound A — — 0.03 0.03 1,390 Example 1-6 100 ComparativeCompound A — — 0.10 0.10 1,470 Example 1-7 100 Comparative Comparative —— 0.10 0.10 1,390 Example 1-8 Compound 2*⁵ 100 *¹Compound A:sodium-2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate *²CompoundB: lithium-2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate *³LIM:lithium myristate *⁴Comparative Compound 1: aluminumhydroxy-bis[2.2′methylene-bis(4,6-di-tert-butylphenyl)phosphate]*⁵Comparative Compound 2: sodium benzoate

According to Comparative Examples 1-3 to 1-5, the physical propertyimproving effect was poor when any one of the components (A), (B) and(C) of the resin additive composition of the present invention was notincorporated. In addition, from Comparative Example 1-2, it wasconfirmed that the change of the component (B) to a nucleating agentdifferent from that of the resin additive composition of the presentinvention also resulted in poor physical property improving effect.

In contrast, the resin additive compositions of Examples according tothe present invention were all confirmed to have excellent physicalproperty improving effect.

TABLE 2 Amount of resin additive composition with respect to Evaluation100 parts by Crystallization Resin additive mass of resin temperaturecomposition [parts by mass] [° C.] Example 2-1 Resin additive 0.03 128composition of Example 1-2 Example 2-2 Resin additive 0.05 131composition of Example 1-2 Example 2-3 Resin additive 0.1 132.5composition of Example 1-2 Comparative Control 0 123 Example 2-1Comparative Compound A 0.03 125.4 Example 2-2 Comparative Compound A0.05 129.5 Example 2-3 Comparative Compound A 0.1 130.5 Example 2-4

From the results of Comparative Examples 2-2 to 2-4 shown in Table 2, itwas confirmed that, as compared to those cases where Compound A wasincorporated alone, the resin additive compositions of Examplesaccording to the present invention had a higher effect of improving theresin crystallization temperature.

Next, with regard to resin additive compositions, the effect of being ina pellet form and that of being in a powder form were evaluated.

By manual blending, 100 parts by mass of a polypropylene block copolymerhaving a melt flow rate of 25 g/10 min at 230° C. was blended for 5minutes with the respective resin additive compositions shown in Table 3below. Then, using twin screw extruder (PCM-30, manufactured by IkegaiCorp.), the resulting mixtures were each granulated under processingconditions of a temperature of 240° C. and a screw speed of 160 rpm,whereby pellets of synthetic resin compositions were obtained.

Using an injection molding machine (EC100-2A; manufactured by ToshibaMachine Co., Ltd.), the thus obtained pellets were each injection-moldedat an injection temperature of 230° C. and mold temperature of 50° C. toprepare test pieces of 10 mm in width, 80 mm in length and 4 mm inthickness. Immediately after the injection molding, the thus obtainedtest pieces were conditioned for at least 48 hours in an incubatorhaving an inner temperature of 23° C., and the flexural modulus wasmeasured in accordance with the test method of ISO178. The resultsthereof are shown in Table 3 below.

TABLE 3 Amount of resin additive composition Flexural Flexural withrespect to 100 modulus in modulus in Resin additive parts by mass ofresin pellet form powder form composition [parts by mass] [MPa] [MPa]Example 3-1 Resin additive 0.05 1,460 1,530 composition of Example 1-4Example 3-2 Resin additive 0.1 1,510 1,560 composition of Example 1-4Comparative Control — 1,190 1,190 Example 3-1 Comparative Compound A0.05 1,260 1,430 Example 3-2 Comparative Compound A 0.1 1,350 1,470Example 3-3

According to Comparative Example 3-2, a nucleator effect was hardlyobtained when Compound A alone was incorporated in an amount of 0.05parts by mass with respect to 100 parts by mass of the pellet formpolypropylene block copolymer. On the other hand, the resin additivecompositions of Examples according to the present invention wereconfirmed to be capable of imparting the pellet form polypropylene blockcopolymer with a nucleator effect even at a low amount.

Next, the effects of using the resin additive composition of the presentinvention in a pellet form resin additive composition will be described.

Production Example 1

sodium-2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate 9.5% by masslithium-2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate 9.5% bymass lithium myristate 9.5% by mass phenolic antioxidant:tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propynyloxymethyl]methane28.6% by mass phosphorus-based antioxidant:tris(2,4-di-tert-butylphenyl)phosphite 28.6% by mass catalystdeactivator: calcium stearate 14.3% by mass

After mixing these materials in accordance with the above formulationusing a Henschel mixer (FM200, manufactured by Mitsui Mining Co., Ltd.)at 1,000 rpm for 1 minute, the resulting mixture was processed usingtwin screw extruder (PCM-30, manufactured by Ikegai Corp.) under theconditions where the cylinder temperature was set to be 30° C. at thesample inlet, 130° C. in the center and 100° C. in the vicinity of theproduct outlet and the extrusion screw rotation speed was set to be 60rpm, whereby a pellet form resin additive composition was produced.

It is noted here that the formulation of this resin additive compositioncorresponds to that of the resin additive composition evaluated inExample 1-4.

Comparative Production Example 1

sodium-2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate 28.5% bymass phenolic antioxidant: 28.6% by masstetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propynyloxymethyl]methanephosphorus-based antioxidant: tris(2,4-di-tert-butylphenyl)phosphite28.6% by mass catalyst deactivator: calcium stearate 14.3% by mass

After mixing these materials in accordance with the above formulationusing a Henschel mixer (FM200, manufactured by Mitsui Mining Co., Ltd.)at 1,000 rpm for 1 minute, the resulting mixture was processed usingtwin screw extruder (PCM-30, manufactured by Ikegai Corp.) under theconditions where the cylinder temperature was set to be 30° C. at thesample inlet, 130° C. in the center and 100° C. in the vicinity of theproduct outlet and the extrusion screw rotation speed was set to be 60rpm, whereby a pellet-form resin additive composition was produced.

Comparative Production Example 2

lithium-2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate 28.5% bymass phenolic antioxidant:tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propynyloxymethyl]methane28.6% by mass phosphorus-based antioxidant:tris(2,4-di-tert-butylphenyl)phosphite 28.6% by mass catalystdeactivator: calcium stearate 14.3% by mass

After mixing these materials in accordance with the above formulationusing a Henschel mixer (FM200, manufactured by Mitsui Mining Co., Ltd.)at 1,000 rpm for 1 minute, the resulting mixture was processed usingtwin screw extruder (PCM-30, manufactured by Ikegai Corp.) under theconditions where the cylinder temperature was set to be 30° C. at thesample inlet, 130° C. in the center and 100° C. in the vicinity of theproduct outlet and the extrusion screw rotation speed was set to be 60rpm, whereby a pellet form resin additive composition was produced.

Production Example 2 (Production of Test Sample A)

The pellet of the resin additive composition produced in ProductionExample 1 was added to 100 parts by mass of a homopolypropylene having amelt flow rate of 8 g/10 min at 230° C. such thatsodium-2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate,lithium-2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate and lithiummyristate were incorporated in a total of 0.1 parts by mass, and theresultant was granulated using twin screw extruder (PCM-30, manufacturedby Ikegai Corp.) at a temperature of 240° C. and a screw speed of 160rpm to obtain a pellet of a synthetic resin composition (test sample A:pellet form).

Further, a powder form resin additive composition having the sameformulation as the pellet produced in Production Example 1 wasgranulated under the same conditions to obtain a pellet of a syntheticresin composition (test sample A: powder).

Comparative Production Example 3 (Production of Test Sample B)

A pellet of a synthetic resin composition (test sample B: pellet form)was produced in the same manner as in Production Example 2, except thatthe pellet of the resin additive composition produced in ProductionExample 1 was changed to the pellet of the resin additive compositionobtained in Comparative Production Example 1 and that the pellet wasadded such thatsodium-2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate wasincorporated in an amount of 0.1 parts by mass.

Further, a powder form resin additive composition having the sameformulation as the pellet produced in Comparative Production Example 1was granulated under the same conditions to obtain a pellet of asynthetic resin composition (test sample B: powder).

Comparative Production Example 4 (Production of Test Sample C)

A pellet of a synthetic resin composition (test sample C: pellet form)was produced in the same manner as in Production Example 2, except thatthe pellet of the resin additive composition produced in ProductionExample 1 was changed to the pellet of the resin additive compositionobtained in Comparative Production Example 2 and that the pellet wasadded such thatlithium-2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate wasincorporated in an amount of 0.1 parts by mass.

Further, a powder form resin additive composition having the sameformulation as the pellet produced in Comparative Production Example 2was granulated under the same conditions to obtain a pellet of asynthetic resin composition (test sample C: powder).

(Flexural Modulus)

Using an injection molding machine (EC100-2A; manufactured by ToshibaMachine Co., Ltd.), the pellets obtained above were eachinjection-molded at an injection temperature of 230° C. and moldtemperature of 50° C. to prepare test pieces having a size of 80 mm×10mm×4 mm. After leaving these test pieces in a 23° C. incubator for atleast 48 hours, the flexural modulus (MPa) of each test piece wasmeasured in accordance with ISO178. The results thereof are shown inTable 4 below.

(Heat Deflection Temperature)

Using an injection molding machine (EC100-2A; manufactured by ToshibaMachine Co., Ltd.), the pellets obtained above were eachinjection-molded at an injection temperature of 230° C. and moldtemperature of 50° C. to prepare test pieces having a size of 80 mm×10mm×4 mm. After leaving these test pieces in a 23° C. incubator for atleast 48 hours, the Heat Deflection Temperature (° C.) of each testpiece was measured in accordance with ISO75 (load: 1.8 MPa). The resultsthereof are shown in Table 4 below.

It is noted here that the units of the numerical values shown in Table 4below are parts by mass.

TABLE 4 Comparative Comparative Production Production Production Example2 Example 3 Example 4 Test sample A Test sample B Test sample CPolypropylene resin 100 100 100 Component (A) 0.033 0.1 Compound AComponent (B) 0.033 0.1 Compound B Component (C) 0.033 LIM Phenolicantioxidant 0.1 0.1 0.1 AO-60*⁶ Phosphorus-based 0.1 0.1 0.1 antioxidant2112*⁷ Catalyst deactivator 0.05 0.05 0.05 Ca-St*⁸ Flexural modulus[MPa] 2,090 1,990 1,890 (pellet form) Flexural modulus [MPa] 2,110 2,0401,950 (powder) HDT [° C.] (pellet form) 115 109 105 HDT [° C.] (powder)115 112 107 *⁶AO-60:tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propynyloxymethyl]methane*⁷2112: tris(2,4-di-tert-butylphenyl)phosphite *⁸Ca-St: calcium stearate

According to Comparative Production Examples 3 and 4, as compared to thecases where a powder form resin additive composition was incorporated,the physical properties were markedly reduced in the pellet form resinadditive compositions containing only the component (A) or (B) as acrystal nucleating agent component.

On the other hand, from Production Example 2, it was confirmed that theresin additive composition according to the present invention in apellet form had comparable physical properties and exhibited excellentdispersion in a resin as compared to the case where the resin additivecomposition was incorporated in a powder form.

1. A resin additive composition comprising: (A)sodium-2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate; (B) alithium phosphate compound represented by the following Formula (1); and(C) at least one fatty acid metal salt represented by the followingFormula (2), wherein a content of said component (B) is in the range of25 to 400 parts by mass with respect to 100 parts by mass of saidcomponent (A); and wherein a content of said component (C) is in therange of 10 to 50 parts by mass with respect to 100 parts by mass ofsaid components (A) and (B):

wherein, R¹ to R⁴ each represent a tert-butyl group; and R⁵ represents amethylene group;

wherein, R⁶ represents an unsubstituted or hydroxy-substituted alkylgroup having 7 to 21 carbon atoms; M represents lithium; and n is 1,representing the valence of said metal atom M.
 2. The resin additivecomposition according to claim 1, further comprising (D) a phenolicantioxidant in an amount of 10% by mass to 50% by mass with respect to atotal amount of the resin additive composition.
 3. The resin additivecomposition according to claim 2, wherein said resin additivecomposition is in a pellet form.
 4. A synthetic resin compositioncomprising: a polyolefin resin; (A)sodium-2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate; (B) alithium phosphate compound represented by the following Formula (1); and(C) at least one fatty acid metal salt represented by the followingFormula (2), wherein the content of said component (B) is in the rangeof 25 to 400 parts by mass with respect to 100 parts by mass of saidcomponent (A); and wherein the content of said component (C) is in therange of 10 to 50 parts by mass with respect to 100 parts by mass ofsaid components (A) and (B):

wherein, R¹ to R⁴ each represent a tert-butyl group; and R⁵ represents amethylene group;

wherein, R⁶ represents an unsubstituted or hydroxy-substituted alkylgroup having 7 to 21 carbon atoms; M represents lithium; and n is 1,representing the valence of said metal atom M.
 5. The synthetic resincomposition according to claim 4, wherein the content of the totalamount of said components (A) and (B) is in the range of 0.001 to 5parts by mass with respect to 100 parts by mass of said polyolefinresin.
 6. A molded article obtained from the synthetic resin compositionaccording to claim
 4. 7. A molded article obtained from the syntheticresin composition according to claim 5.